Femtosecond Time-Resolved Photoelectron Spectroscopy

Stolow, Albert; Bragg, Arthur E.; Neumark, Daniel M.

doi:10.1021/cr020683w

Cited by 664 publications

(626 citation statements)

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“…The RCB is highly anisotropic with maxima centred at localised charge sites. Classically then, an electron ejected from such a system would experience the anisotropic RCB providing a directional force onto the outgoing 50 electron, that can ultimately "guide" the photoelectron in a specific direction. Such directional emission can, in principle, be observed through PE imaging.…”

Section: Photoelectron Angular Distributions As a Measure Of Moleculamentioning

confidence: 99%

“…However naïve this picture may be because electrons are quantum particles, it appears to capture the physics remarkably well. Quantum mechanically, a PE wave is composed of partial 50 waves which interfere to produce the asymptotic PE angular distribution commonly observed in anions or neutrals. 73 In MCAs, it appears that this inherent anisotropy is trumped by the influence of the RCB and classical mechanics dominates.…”

Section: Photoelectron Angular Distributions As a Measure Of Moleculamentioning

confidence: 99%

“…24 This yields an RCB height of 0.84 eV, which corresponds to κ = 1.31 and this is likely correlated with the delocalised hole. A key point to note is that the height of the RCB effectively provides a distance measurement between well-localised charge sites in a molecular 50 MCA. Hence, PE spectroscopy can be used as an intramolecular ruler.…”

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confidence: 99%

“…Time-resolved (TR) PE spectroscopy has been instrumental in understanding excited state processes in gas-phase molecules and clusters and is particularly powerful in 75 anions as the detachment energies are often sufficiently low to enable the monitoring of the entire reaction coordinate including the ground state of the anion or MCA. [50][51][52][53] The first TR PE spectroscopy experiments on MCAs were performed by the Kappes group 30,54 and the first direct observation of an excited 80 state decay by electron tunnelling through the RCB was on the phthalocyanine-tetrasulfonate tetra-anion, H 2 PcSO 3 4-, following Q-band excitation. 30 The excited state lifetime was measured to be ~70 ps.…”

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confidence: 99%

“…If tunnelling is fast, then there will be relatively little internal vibration redistribution and the tunnelling is adiabatic. 50 Consequently, the transition appears as a diagonal transition. Similar features have also been seen in the PE spectroscopy of monoanions when the photon is resonant with a transition above threshold.…”

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Excited states of multiply-charged anions probed by photoelectron imaging: riding the repulsive Coulomb barrier

Verlet

Horke

Chatterley

2014

Phys. Chem. Chem. Phys.

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Section: Photoelectron Angular Distributions As a Measure Of Moleculamentioning

confidence: 99%

Section: Photoelectron Angular Distributions As a Measure Of Moleculamentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Excited states of multiply-charged anions probed by photoelectron imaging: riding the repulsive Coulomb barrier

Verlet

Horke

Chatterley

2014

Phys. Chem. Chem. Phys.

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Ultrafast Spectroscopy

Kühn

Lochbrunner

2009

Digital Encyclopedia of Applied Physics

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This chapter introduces the concepts, theoretical approaches, and experimental techniques of ultrafast spectroscopy. By pushing the time resolution to a few femtoseconds the observation of atomic and molecular motions in real time becomes possible. This is illustrated by means of applications including molecular dynamics from isolated diatomics via clusters to biomolecules as well as processes in semiconductors and at surfaces. Perspectives are given on the emerging fields of attosecond physics and time‐resolved diffraction techniques.

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Time‐Resolved Spectroscopy: Instrumentation and Applications

Ariese

Roy

Venkatraman

et al. 2017

Encyclopedia of Analytical Chemistry

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Light–matter interaction may lead to three fundamental phenomena, viz. (i) absorption, (ii) emission, and (iii) scattering. Spectroscopic techniques based on these phenomena are used to characterize the materials of interest, not only stable compounds but also short‐lived species during molecular transformations. Determining the electronic and molecular structure of the transient species is crucial in order to understand various photochemical, physical, and biological processes of fundamental and technological importance. Identifying various redox species during photosynthesis, understanding the photoinduced charge transfer process in solar cells, unraveling the photochemistry of vision that involves photoisomerization of retinal, etc. require spectroscopic techniques that can resolve various transient species in time and were practically impossible until the advent of pulsed lasers. The absorption of a photon by a molecule may initiate a cascade of dynamic molecular events, namely vibrational relaxation (VR), solvation dynamics, internal conversion (IC), intersystem crossing (ISC), electron transfer, isomerization reactions, etc., which can occur at femtosecond (fs) to picosecond (ps) timescales. Bimolecular reaction dynamics in liquids, such as H‐atom abstraction reaction, are typically diffusion controlled and therefore can be observed at nanosecond (ns) timescales. Therefore, time‐dependent (time‐resolved) spectroscopy has been an exquisite tool to follow the molecular dynamics after an initial phototrigger. Apart from studying molecular dynamics, time resolution can also be used to distinguish conformers, isomers or enantiomers, or distinguish identical compounds in different environments. It can also be applied to suppress unwanted signals occurring at different timescales, for instance fluorescence suppression in Raman experiments, or selectively detect compounds deeper inside a sample. In this article, we first give an introduction to the fundamentals of time‐resolved electronic absorption, spontaneous excited‐state resonance Raman, and coherent Raman scattering and emission techniques, spanning the range from femtosecond to microsecond timescales. Important technical aspects of time‐resolved spectroscopic equipment are also discussed. We then present some examples of cis–trans isomerization, thermal equilibrium of the two lowest triplet states, H‐atom abstraction reactions, etc. and demonstrate the molecular dynamic events after an initial phototrigger by a comprehensive kinetic analysis of the peak position, width and intensity of the marker bands in the time‐resolved electronic absorption, and Raman and emission spectra.

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Femtosecond Time-Resolved Photoelectron Spectroscopy

Cited by 664 publications

References 270 publications

Excited states of multiply-charged anions probed by photoelectron imaging: riding the repulsive Coulomb barrier

Excited states of multiply-charged anions probed by photoelectron imaging: riding the repulsive Coulomb barrier

Ultrafast Spectroscopy

Time‐Resolved Spectroscopy: Instrumentation and Applications

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